KR20110056316A - Pigment dispersion composition for color filters, and color filters - Google Patents

Abstract

A pigment dispersion composition for color filters containing a colorant, a resin, and an organic solvent capable of dissolving the resin. Obtained by polymerizing the modified polyamine (B) which made vinyl copolymer (B-1) react with the amino group of polyamine, and at least 1 type of polymerizable unsaturated monomer (C) soluble in a non-aqueous solvent and insoluble or poorly soluble after superposition | polymerization. Pigment dispersion composition for color filters, and a color filter containing the modified pigment (D) which has a polymer (P). A general purpose pigment is used to provide a color filter excellent in dispersion stability and excellent in contrast.

Description

Pigment dispersion composition and color filter for color filters {PIGMENT DISPERSION COMPOSITION FOR COLOR FILTERS, AND COLOR FILTERS}

This invention relates to the pigment dispersion composition for color filters which used the pigment as a coloring material.

In general, the color filter has a cyan, magenta, and yellow color in the reflective type so as to selectively transmit three primary colors of red, green, and blue light in the case of a transmission type on a substrate provided with a mesh-shaped light shielding thin film layer called a black matrix. In order to selectively reflect the three primary colors of, a colored cured coating layer corresponding to each color is formed in each mesh of the black matrix, and the respective meshes are regularly arranged. In addition, "mesh" of the said black matrix is called "pixel."

The color filter is used for color object imaging elements, color displays, such as a liquid crystal color display and a color CRT. In recent years, a high contrast is calculated | required by the request to high quality of a color filter.

In the manufacturing method of a color filter, the dyeing method which uses dye as a coloring agent was the mainstream in the early stage, but in order to respond to the said requirement, the pigment dispersion method using the pigment excellent in heat resistance, light resistance, chemical resistance, etc. has become the mainstream in recent years. . In this pigment dispersion method, the pigment dispersion resist which added the photopolymerizable monomer and the photoinitiator to the pigment dispersion composition which disperse | distributed the pigment using the dispersing agent in binder resin was apply | coated on a base material, it dried, and exposed through the photomask, The photolithographic method of forming a cured coating film layer of a pigment dispersion resist in a pixel portion by performing development and thermosetting treatment is generally widely performed.

As a method of manufacturing a color filter by this "photolithographic method", for example, a pigment, a coupling agent, a main chain or a side chain contains an acrylic copolymer having an N, N-disubstituted amino group and an acid group, and a solvent, The pigment dispersion composition for color filters which is excellent in transparency, developability, and light resistance, and is excellent in storage stability is proposed (for example, refer patent document 1). However, also in the said method, it cannot necessarily fully satisfy the required characteristic about recent higher dispersion stability, long term storage stability, transparency, etc.

On the other hand, when kneading | mixing a general purpose pigment, resin, and an organic solvent as a raw material, the said raw material is made, making solid content ratio (mass conversion) of the said pigment and the said resin into a specific ratio, and evaporating and removing the said organic solvent. The method of obtaining the pigment dispersion liquid for color filters excellent in dispersion stability, long-term storage stability, transparency, etc. by kneading with a planetary mixer is known (for example, refer patent document 2). However, the method is kneaded while constantly monitoring the solid content ratio, or because it is a kneaded dough, a long time kneading is necessary and cannot be called a simple kneading method.

[Prior Art Literature]

[Patent Documents]

Patent Document 1: Japanese Patent Application Laid-Open No. 2003-64293 (paragraphs [0002] to [0008])

Patent Document 2: Japanese Patent Application Laid-Open No. 2006-111752

SUMMARY OF THE INVENTION [

[Problem to Solve Invention]

An object of the present invention is to provide a pigment dispersion composition for color filters that provides a color filter that is excellent in dispersion stability and excellent in contrast by using a general-purpose pigment.

[Means for solving the problem]

The inventor firstly has a polymer obtained on the surface of a pigment by polymerizing a polymer containing a polymerizable unsaturated group soluble in a nonaqueous solvent and at least one polymerizable unsaturated monomer soluble in a nonaqueous solvent and insoluble or poorly soluble after polymerization. It is discovered that it is excellent in dispersion stability when it invents the pigment characterized by Unexamined-Japanese-Patent No. 2008-88211, and adjusts it as the pigment dispersion composition for color filters using the said pigment (Japanese Patent Application Laid-Open No. 2009-529445).

The present inventors also apply a modified pigment using a polymer having a specific structure to a pigment dispersion composition for color filters instead of a polymer containing a polymerizable unsaturated group soluble in a nonaqueous solvent, thereby providing excellent dispersion stability and color filter pixels. It was found that a color filter having excellent negative contrast was obtained, and completed the present invention.

That is, this invention is a pigment dispersion composition for color filters containing a colorant, resin, and the organic solvent which can melt | dissolve the said resin, As a colorant,

On the pigment (A) surface,

Modified polyamine (B) which reacted the vinyl copolymer (B-1) which has the functional group which reacts with an amino group to form an amide bond at one end, and was made to react with the amino group of a polyamine,

Polymer (P) obtained by polymerizing at least one polymerizable unsaturated monomer (C) that is soluble in a nonaqueous solvent and insoluble or poorly soluble after polymerization.

It provides the pigment dispersion composition for color filters using the modified pigment (D) having a.

Moreover, this invention provides the color filter using the pigment dispersion composition for color filters of the said base material.

[Effects of the Invention]

According to this invention, the pigment dispersion composition for color filters which provides the color filter which is excellent in dispersion stability and excellent in contrast using a general purpose pigment can be provided.

[Mode for Carrying Out the Invention]

(Modified Pigment (D))

The modified pigment (D) used as the colorant in the present invention is a polyamine having a vinyl copolymer (B-1) having a functional group that reacts with a general-purpose pigment (A), a non-aqueous solvent, and an amino group to form an amide bond at one end thereof. By so-called in-situ polymerization, in the presence of a modified polyamine (B) reacted with an amino group, the polymerizable polymerizable unsaturated monomer (C) is soluble in the nonaqueous solvent and insoluble or poorly soluble after polymerization. You can get it.

(Pigment (A))

Pigment (A) used by this invention is at least 1 sort (s) of pigment chosen from well-known conventional organic pigment or an inorganic pigment. Moreover, in this invention, any of an untreated pigment and a process pigment can be applied.

As the pigment (A), commercially available pigments conventionally used for color filters, and the "Color Index Manual" (Latest Pigment Handbook Japan Pigment Technology Association, 1977) "Latest Pigment Application Technology" (CMC Publishing, 1986) And known conventional pigments described in "Printing Ink Technology" (CMC Publishing, 1984).

Especially as a pigment used universally in a color filter, Specifically, for example, C.I. Pigment Red 254 or C.I. Pigment Red 177 or C.I. Red pigments such as Pigment Orange 71, C.I. Pigment Green 36, C.I. Pigment Green 58 or C.I. Green pigments such as Pigment Green 7, C.I. Pigment Blue 15: 6 or C.I. Blue pigments such as Pigment Blue 22, C.I. Pigment Violet 23 or C.I. Violet pigments, such as pigment violet 50, and C.I. Pigment Yellow 138, C.I. Pigment Yellow 150 or C.I. Yellow pigments such as Pigment Yellow 20, C.I. Pigment black 7, black pigments, such as carbon black and titanium black, etc. are mentioned, These pigments may be used independently, and may mix and use two or more types as needed.

Generally, although the transparency of the cured coating film of the pigment dispersion liquid for color filters becomes small, the particle size of the pigment to contain becomes large, but it is preferable to make the primary particle diameter into the range of 10-80 nm, and to make it the range of 30-50 nm. Particularly preferred. If the primary particle size is less than 10 nm, the cohesiveness of the pigment becomes high, which makes it difficult to disperse the particles. If the primary particle size exceeds 80 nm, transparency decreases.

Among these, since the effect of this invention is exhibited to the maximum, especially C.I. It is preferable to use Pigment Green 58.

(Non-aqueous solvent)

The nonaqueous solvent used by this invention is an organic solvent which makes an aliphatic and / or alicyclic hydrocarbon solvent essential. As the aliphatic and / or alicyclic hydrocarbon solvent, for example, n-hexane, n-heptane, n-octane, "Loose" or "Mineral Spirit EC" manufactured by Shell Chemicals, "Axon Mobil Chemicals" Isoper C, iso E, iso G, iso H, iso L, iso M, naphtha 3, naphtha 5 or naphtha 6 No. 7, Solvent No. 7, IP Solvent 1016, IP Solvent 1620, IP Solvent 2028, or IP Solvent 2835 of Idemitsu Seki Yugaku Co., Ltd. "White sol", "Marukazol 8" by Maruzen Seki Yugaku Co., Ltd., etc. are mentioned.

Moreover, you may mix and use the other organic solvent in the range which does not impair the effect of this invention. As such an organic solvent, For example, Aromatic hydrocarbon solvents, such as "swazole 100-150", toluene, or xylene of Maruzen Seki Yugaku Co., Ltd .; Esters such as methyl acetate, ethyl acetate, n-butyl acetate or amyl acetate; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone or cyclohexanone; Or alcohols such as methanol, ethanol, n-propanol, i-propanol or n-butanol.

When using in mixture, it is preferable to make the usage-amount of the said aliphatic and / or alicyclic hydrocarbon solvent into 50 mass% or more, More preferably, it is 60 mass% or more.

(Modified Polyamine (B))

The modified polyamine (B) used in the present invention is a vinyl copolymer (B-1) having a functional group that reacts with an amino group to form an amide bond at its one end (hereinafter, "functional group that reacts with an amino group to form an amide bond). "Vinyl copolymer (B-1)" at one end is merely a vinyl copolymer (B-1)), and is a modified polyamine (B) in which the amino group of the polyamine is reacted. It is known that polyamine has high adsorptivity to a pigment generally, and the modified polyamine (B) of this invention raises dispersion stability of a pigment in a hydrophobic solvent. As a result, since the dispersed particle diameter of the modified pigment (D) obtained by superposing | polymerizing the polymerizable unsaturated monomer (C) mentioned later on the pigment surface becomes thinner, it is considered preferable.

(Polyamine)

The polyamine used by this invention is a polymer which has a repeating unit which has a primary or secondary amino group. As such polyamine, it is preferable that it is at least 1 sort (s) chosen from the group which consists of polyallylamine, polyvinylamine, and polyethyleneimine. Moreover, the copolymer of polyallylamine, polyvinylamine, or polyethyleneimine and another polymerizable monomer may be sufficient.

When using the copolymer of polyallylamine, polyvinylamine, or polyethyleneimine and another polymerizable monomer, the amine number of the polyamine of this invention has preferable 50 or more, and 300 or more is more preferable. If the amine value is less than 50, there is a fear that the dispersibility of the modified pigment obtained due to insufficient adsorptive power to the pigment. These polyamines may use only one type, and may mix and use plurality. Among these, polyallylamine or polyethyleneimine is preferable from a viewpoint of industrial availability, and polyallylamine is mentioned as a most preferable thing especially. The reason for this is that the polyethyleneimine generally has a branched polymer structure, and since the polyallylamine has a linear polymer structure, it is considered that the anchoring effect of the amine to the pigment is high.

The number average molecular weight of the polyamine in this invention becomes like this. Preferably it is 150-100,000, More preferably, it is 600-20,000. If the number average molecular weight of the polyamine used in the present invention is less than 150, there is a possibility that the pigment dispersion is difficult due to insufficient adsorptive power to the pigment, while the amount of the polyamine exceeds 100,000 to increase the viscosity upon reaction with the vinyl polymer. And gelation may be caused, and the molecular weight of the polymer is too large, and there is a fear that the dispersibility may decrease due to aggregation of the pigments.

(Polyallylamine)

The polyallylamine used by this invention may be obtained by superposing | polymerizing allylamine by a well-known method in presence of a polymerization initiator, and in some cases, chain transfer catalyst, and may use a commercial item. As a commercial item, it is marketed as a polyallylamine series, such as PAA-01, PAA-03, PAA-05, PAA-15, PAA-10C, for example from Nitto Boseki Corporation.

(Polyvinylamine)

In the polyvinylamine used in the present invention, for example, N-vinylformamide is polymerized by a known method in the presence of a polymerization initiator and, in some cases, in a chain transfer catalyst, and then subjected to a hydrolysis reaction. It can obtain by well-known various methods.

Polyethyleneimine

The polyethyleneimine used by this invention may be obtained by superposing | polymerizing ethylene imine by a well-known method, and may use a commercial item. As a commercial item, Nippon Shokubai Co., Ltd. is marketed as polyethyleneimine series, such as SP-003, SP-006, SP-012, SP-018, SP-200, and P-1000, for example.

(Vinyl copolymer (B-1))

In the vinyl copolymer (B-1) used in the present invention, examples of the functional group that reacts with an amino group to form an amide bond include an oxycarbonyl group such as a haloformyl group such as a carboxy group and a chloroformyl group and a methoxycarbonyl group. . Especially, since a carboxyl group can be easily introduce | transduced into a vinyl copolymer, it is preferable.

In order to obtain the vinyl copolymer which has a carboxyl group at one end, the method of coexisting the chain transfer agent which has a carboxyl group at the time of superposition | polymerization, for example is mentioned. Examples of the chain transfer agent having a carboxy group include thiocarboxylic acids such as mercaptoacetic acid, 2-mercaptopropionic acid and 3-mercaptopropionic acid. Moreover, it can also be obtained by the method of synthesize | combining a polymerizable monomer by a living radical polymerization method using the polymerization initiator which has a carboxyl group, such as 4,4'- azobis-4- cyanopentanoic acid.

The polymerizable monomer which becomes a raw material of a vinyl copolymer (B-1) is (meth), such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate, for example. ) Homopolymers of alkyl acrylates or these esters or their esters, alkenylbenzenes such as styrene, α-methylstyrene and vinyltoluene, and also vinyl acetate, vinylpyridine, acrylamide, methacrylamide and methacrylic acid And copolymers with dimethylaminoethyl, N-methylolacrylamide, N-butoxymethylacrylamide (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl and the like. One or two or more of these can be used.

However, it is preferable not to use the functional group which reacts with an amino group, and forms a amide bond, for example, the polymerizable monomer which has a functional group which is high in reactivity with an amino group more than or equal to a carboxy group. The vinyl polymer containing the polymerizable monomer in the raw material is not only the terminal of the vinyl copolymer, but also the functional group is randomly grafted to the main chain of the copolymer, and thus the performance of the modified pigment obtained by gelation or reaction during the reaction with polyallylamine. This may fall. Specifically, polymerizable monomers such as butadiene, isoprene, chloroprene, (meth) acrylic acid, itaconic acid and maleic anhydride have a group having high reactivity with amino groups, and thus, as a raw material of the vinyl copolymer (B-1) It is preferable not to use.

Since a liquid crystal display device etc. are required to raise display characteristics, such as visibility, more, it may be required to control the retardation value of the colored pixel layer which comprises a color filter. In such a case, since the vinyl copolymer (B-1) contains an alkyl group having 10 to 24 carbon atoms, it is possible to control the retardation value of the pixel in the negative direction. That is, what is necessary is just to use the (meth) acrylic acid ester containing a C10-C24 alkyl group as one of raw materials. The (meth) acrylic acid ester containing an alkyl group having 10 to 24 carbon atoms may be either linear or branched, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, (Meth) acrylate acrylic, cetyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, etc. can be illustrated. As a quantity which mix | blends the (meth) acrylic acid ester containing such a C10-C24 alkyl group with a vinyl copolymer (B-1), 10-100 mass% is preferable, and its 20-100 mass% is more preferable. Do. When the quantity of the (meth) acrylic acid ester containing a C10-C24 alkyl group is less than 10 mass%, there exists a possibility that a desired retardation value adjusting ability may not be exhibited.

The vinyl copolymer (B-1) can be obtained by heating the above-mentioned various polymerizable monomers in the presence of a polymerization initiator in a reaction vessel and aging as necessary. As reaction conditions, although it changes with a polymerization initiator and a solvent, for example, reaction temperature is 30-150 degreeC, Preferably it is 60-120 degreeC. The polymerization may be performed in the presence of a non-reactive solvent.

Examples of the polymerization initiator include peroxides such as t-butylperoxybenzoate, di-t-butylperoxide, cumene peroxide, acetyl peroxide, benzoyl peroxide and lauroyl peroxide; Azo compounds such as azobisisobutylnitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile and the like.

Examples of the non-reactive solvent include aliphatic hydrocarbon solvents such as hexane and mineral spirits; Aromatic hydrocarbon solvents such as benzene, toluene, xylene and the like; Ester solvents such as butyl acetate; Alcohol solvents such as methanol and butanol; And aprotic polar solvents such as dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, pyridine and the like. You may use these solvents together. These solvents can be used by selecting suitably what the vinyl copolymer (B-1) melt | dissolves.

It is preferable that it is the range of the number average molecular weights 500-100,000, and, as for the molecular weight of the vinyl copolymer (B-1) used by this invention, it is still more preferable that it is the range which is 1000-20,000. If the number average molecular weight is less than 500, a sufficient steric repulsion effect as a pigment dispersant may not be maintained. If the number average molecular weight is more than 100,000, an increase in the viscosity of the vinyl polymer and a decrease in solvent solubility may occur, resulting in a decrease in the performance of the obtained modified pigment. There is a case.

Moreover, the modified polyamine (B) in this invention is one or more selected from the group which consists of a vinyl copolymer (B-1) and following (B-2)-(B-5) to the said polyamine. It is preferable to react a compound.

(b1) A vinyl copolymer having a functional group reacting with an amino group at one end thereof, wherein the amount of functional group, copolymer composition or copolymer composition reacting with the amino group is different from the vinyl copolymer (B-1) (B-). 2).

As said vinyl copolymer (B-2), a vinyl copolymer (B-2-1) is preferable. A vinyl copolymer (B-2-1) is a weight% of the functional group which reacts with the amino group in the one end of the said vinyl copolymer (B-1), and the one end of the said vinyl copolymer (B-2-1). The ratio of the weight% of the functional group reacting with the amino group in the range of 0.4 to 0.8, and the molar ratio (B-1) / (B-2-1) with the vinyl copolymer (B-1) is ( It is preferable to react with modified polyamine so that B-1) / (B-2-1) = 0.25-4.0 (henceforth a vinyl copolymer (B-2-1)).

Moreover, as said vinyl copolymer (B-2), a vinyl copolymer (B-2-2) is preferable. The vinyl copolymer (B-2) is a vinyl copolymer obtained by polymerizing a plurality of vinyl monomers, and the difference between Tg of the vinyl copolymer (B-1) and Tg of the vinyl copolymer (B-2-2) is 20. The molar ratio (B-1) / (B-2-2) of the vinyl copolymer (B-1) and the vinyl copolymer (B-2-2) is not lower than or equal to (° C). It is preferable to react with modified polyamine so that it may be /(B-2-2)=0.25-4.0 (henceforth a vinyl copolymer (B-2-2)).

(b2) (meth) acrylate (B-3) which has a polyalkylene glycol chain (henceforth (meth) acrylate (B-3)). Especially, it is preferable to react with the modified polyamine so that the said polyalkylene glycol chain may be in the ratio of 1 to 30 weight% with respect to the whole molecule | numerator.

(b3) polyester having a functional group reacting with an amino group at one end, polyamide having a functional group reacting with an amino group at one end, or polyesteramide (B-4) having a functional group reacting with an amino group at one end (hereinafter polymer (B-4)). Especially, it is preferable that the said modified polyamine reacts with a modified polyamine so that these residues may have a ratio of 1-50 weight% with respect to the whole molecule | numerator.

(b4) monocarboxylic acid or (meth) acrylate (B-5). Especially, it is preferable to react with modified polyamine so that these residue may be in the ratio of 1 to 30 weight% with respect to the whole molecule | numerator.

((b1) vinyl copolymer (B-2-1))

The said vinyl copolymer (B-2-1) has a functional group which reacts with an amino group at one end, and is a copolymer different from the said vinyl copolymer (A), The one end of the said vinyl copolymer (B-1) The ratio of the weight% of the functional group reacting with the amino group in the group and the weight% of the functional group reacting with the amino group in the one end of the vinyl copolymer (B-2-1) is in the range of 0.4 to 0.8, and the vinyl Reacting with modified polyamine so that molar ratio (B-1) / (B-2-1) with copolymer (B-1) is (B-1) / (B-2-1) = 0.25-4.0 It is preferable.

Specifically, a vinyl copolymer (B-2-1) is a vinyl copolymer which has a carboxy group, and is a copolymer from which the molecular weight differs from the said vinyl copolymer (B-1). Adjustment of molecular weight is performed according to content of the carboxyl group in the one end of a vinyl copolymer, It is preferable that the weight% of the carboxyl group in a vinyl copolymer is the range of 1-10, and the said vinyl copolymer (B-1) It is preferable that the ratio of the weight% of the carboxyl group at one end of the compound to the weight% of the carboxyl group at the one end of the vinyl copolymer (B-2-1) is in the range of 0.4 to 0.8. The vinyl copolymer (B-2-1) has a higher molecular weight than the vinyl copolymer (B-1)).

In addition, the ratio of the vinyl polymer (B-2-1) residue (wherein the vinyl polymer (B-2-1) residue) refers to the remaining portion to which the carboxyl group reacts) and the vinyl copolymer (B-1) residue are such vinyl. It is preferable that molar ratio (B-1) / (B-2-1) with copolymer (B-1) is (B-1) / (B-2-1) = 0.25-4.0.

((b1) vinyl copolymer (B-2-2))

The vinyl copolymer (B-2-2) is a vinyl obtained by polymerizing a plurality of vinyl monomers, and the difference between the Tg of the vinyl copolymer (B-1) and the Tg of the vinyl copolymer (B2) is 20 ° C or higher. Copolymer. In addition, Tg is defined here as the value measured by tB-1n (delta) peak of DSC (differential scanning calorimetry) or dynamic viscoelasticity.

As described above, the molar ratio (B-1) / (B-2-2) of the vinyl copolymer (B-1) and the vinyl copolymer (B-2-2) is (B-1) / ( It is preferable to react with modified polyamine so that B-2-2) = 0.25-4.0.

Specifically, the Tg of the vinyl copolymer (B-2-2) is preferably 100 ° C to -50 ° C, and also varies depending on the Tg of the vinyl copolymer (B-1), but the Tg is 60 ° C to -50 ° C. It is especially preferable that it is ° C.

((b2) (meth) acrylate (B-3))

In said (meth) acrylate (B-3), having polyalkylene glycol chain | strand shows the state of polyalkylene glycol (meth) acrylate. Specifically, polyalkylene glycol is polyethyleneglycol, polypropylene glycol, polybutylene glycol, a mixture thereof, etc. Among these, polyethyleneglycol and polypropylene glycol are preferable.

It is preferable that (meth) acrylate (B-3) is reacted with modified polyamine so that the said polyalkylene glycol chain may be in the ratio of 1 to 30 weight% with respect to the whole molecule | numerator.

((b3) Polymer (B-4))

Specifically, the polymer (B-4) is any of the following polymers (b3-1) to (b3-3).

(b3-1) Polyester which has a functional group which reacts with an amino group at one end,

(b3-2) Polyamides having functional groups reactive to amino groups at one end

(b3-3) Polyester amide having a functional group reactive to an amino group at one end

(b3-1) Polyester which has a functional group which reacts with an amino group at one end is specifically polyester which has a carboxyl group at the terminal. This can be synthesized by the following various methods.

(B-1) an addition reaction for adding a lactone compound to a monocarboxylic acid compound, (b) an addition reaction for adding a lactone compound to a hydroxycarboxylic acid compound, (c) a three component of a monocarboxylic acid compound, a hydroxycarboxylic acid compound and a lactone compound And a condensation reaction for condensation.

(b3-2) The polyamide which has a functional group which reacts with an amino group at one end is specifically a polyamide which has a carboxy group at the terminal. This is prepared from lactams such as ε-caprolactam and ω-laurolactam, and aminocarboxylic acids such as aminocaproic acid and 11-aminoundecanoic acid as raw materials.

(b3-3) The polyesteramide which has a functional group which reacts with an amino group at one end is specifically a cocondensate of ester and amide which have a carboxyl group at the terminal. This can be produced by cocondensing hydroxycarboxylic acid, lactone and the like, aminocarboxylic acid, lactam and the like used in the production of the polyester and polyamide.

It is preferable that the said polymer (B-4) is reacted with modified polyamine so that these residue may be in the ratio of 1-50 weight% with respect to the whole molecule | numerator. A residue here represents the remainder of a polymer part to which a carboxyl group reacted.

((b4) monocarboxylic acid or (meth) acrylate (B-5))

The monocarboxylic acid is not particularly limited as long as it is a compound having one carboxylic acid group in one molecule, specifically, acetic acid, propionic acid, caprylic acid, nonanoic acid, capric acid, octylic acid, lauric acid, myristic acid, and palate. Aromatic monocarboxylic acids, such as aliphatic monocarboxylic acids, such as amic acid, a stearic acid, an isononanoic acid, and an arac acid, benzoic acid, and p-butylbenzoic acid, are mentioned.

Moreover, the (meth) acrylate used for this invention is (meth) acrylic acid, such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate, for example. Homopolymers of alkyl esters or these esters or their esters and alkenylbenzenes such as styrene, α-methylstyrene and vinyltoluene, and also vinyl acetate, vinylpyridine, acrylamide, methacrylamide and dimethyl methacrylate Copolymers with ethyl, N-methylol acrylamide, N-butoxymethyl acrylamide, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, and the like.

It is preferable that the said monocarboxylic acid and the said (meth) acrylate are reacted with the modified polyamine so that these residues may have a ratio of 1-30 weight% with respect to the whole molecule especially. Here, a residue represents the remainder monocarboxylic acid or (meth) acrylate which carboxyl group reacted.

(Reaction of Polyamine with Vinyl Copolymer (B-1))

The reaction of the polyamine with the vinyl copolymer (B-1) or a mixture of the vinyl copolymer (B-1) to the compound (B-5) is, for example, 200 ° C. or less under a nitrogen gas stream. You can do this at You may use well-known polymerization catalysts, such as a tin system and titanium system, for reaction. If necessary, non-reactive solvents such as toluene, xylene, and Solvesso, which are not involved in the reaction, can be used. The used solvent does not necessarily need to be removed.

It is preferable that the graft ratio of the vinyl copolymer (B-1) with respect to a polyamine is about 20 to 95% of range, and it is 30 to 90% of range of affinity with a diluting solvent and film-forming resin. It is especially preferable because it is excellent in the balance of affinity with a pigment. In addition, a graft rate shows the reaction amount of the carboxy group of a vinyl copolymer (B-1) with respect to the total amount of the amino group which a polyamine has, and the vinyl copolymer which passed the amide bond which the modified polyamine of this invention has (B-1) ) Remaining chain (The vinyl copolymer (B-1) remaining chain here means% of remainder which the carboxy group reacted.).

When the said vinyl copolymer (B-1) residue which the said modified polyamine has is less than 20%, aggregation of pigments will occur easily, and the lack of a viscosity fall effect and an ink film may arise. Moreover, when the said vinyl copolymer (B-1) residue which the said modified polyamine has exceeds 95%, the amino group which is a functional group adsorb | sucking with a pigment runs short, and there exists a tendency for dispersion stability to fall depending on a pigment, and also a viscosity Lack of a deterioration effect and a defect may arise in an ink film.

(Reaction of polyamine with one or more compounds selected from the group consisting of the above (B-2) to (B-5))

The reaction of the polyamine with one or more compounds selected from the group consisting of the above (B-2) to (B-5) can be performed at 200 ° C. or lower, for example, under a nitrogen gas stream. You may use well-known polymerization catalysts, such as a tin system and titanium system, for reaction. If necessary, non-reactive solvents such as toluene, xylene, and sorbetso, which are not involved in the reaction, can be used. The used solvent does not necessarily need to be removed, and can be used as it is as one component of the pigment dispersant.

The reaction of the polyamine with one or more compounds selected from the group consisting of the above (B-2) to (B-5) may be performed simultaneously with the vinyl copolymer (B-1) or sequentially.

(Other ingredients)

The modified polyamine (B) used in this invention may contain the non-reactive solvent used at the time of manufacture of a modified polyamine (B), and also removes the other solvent after distilling off the non-reactive solvent used at the time of manufacture. You can add a new one.

In order to have a crosslinking point with the polymer (P) obtained by superposing | polymerizing the polymerizable unsaturated monomer (C) mentioned later to the modified polyamine (B) used by this invention, it is also preferable to introduce a polymerizable unsaturated group. This is because it becomes possible to coat the pigment surface more firmly by crosslinking the polymer (P) and the modified polyamine (B). As a method of introducing a polymerizable unsaturated group into the modified polyamine (B), for example, a method of introducing a polymerizable unsaturated group by adding glycidyl methacrylate after reacting the polyamine with the vinyl copolymer (B-1) There is this.

(Polymerizable unsaturated monomer (C) soluble in nonaqueous solvent and insoluble or poorly soluble after polymerization)

The polymerizable unsaturated monomer (C) which is soluble in the nonaqueous solvent used in the present invention and insoluble or poorly soluble after polymerization is specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, So-called n-propyl (meth) acrylate or i-propyl (meth) acrylate or olefins such as (meth) acrylonitrile, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl fluoride or vinylidene fluoride Vinyl monomers having no reactive polar group (functional group); (Meth) acrylamide, dimethyl (meth) acrylamide, Nt-butyl (meth) acrylamide, N-octyl (meth) acrylamide, diacetone acrylamide, dimethylaminopropyl acrylamide or alkoxylated N-methylolated (meth Amide bond-containing vinyl monomers such as acrylamide; Dialkyl [(meth) acryloyloxyalkyl] phosphates or (meth) acryloyloxyalkyl acid phosphates, or dialkyl [(meth) acryloyloxyalkyl] phosphites or (meth) acryloyl Oxyalkyl acid phosphites; Epoxy group-containing vinyl monomers and phosphoric acid, such as alkylene oxide adducts of the (meth) acryloyloxyalkyl acid phosphates or acid phosphates, glycidyl (meth) acrylates and methylglycidyl (meth) acrylates; Or phosphorus atom-containing vinyl monomers such as 3-chloro-2-acidphosphoxypropyl (meth) acrylate, including ester compounds with phosphorous acid or acidic esters thereof; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl ( Meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, di-2-hydroxyethyl fumarate or mono-2-hydroxyethyl monobutyl Hydroxy of polymerizable unsaturated carboxylic acids, such as a fumarate, a polypropylene glycol, polyethyleneglycol mono (meth) acrylate, or a "fraxel FM, FA monomer" (caprolactone addition monomer by Daicel Chemical Co., Ltd.) Alkyl esters or adducts of these with ε-caprolactone, and the like, as well as unsaturated mono- or dicarboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid or citraconic acid, Polymerizable unsaturated carboxylic acids such as monoesters of dicarboxylic acids and monohydric alcohols, or the polymerizable unsaturated carboxylic acid hydroxyalkyl esters with maleic acid, succinic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, and benzenetricarboxylic acid And various unsaturated carboxylic acids such as adducts with anhydrides of polycarboxylic acids such as benzenetetracarboxylic acid, "hymic acid", tetrachlorophthalic acid or dodecenyl succinic acid, and "kajura E", palm oil fatty acid glycidyl ester or octylic acid Monoglycidyl esters of monovalent carboxylic acids such as cylyl esters or adducts of monoepoxy compounds such as butylglycidyl ether, ethylene oxide, or propylene oxide, or adducts of these with ε-caprolactone or hydroxy Hydroxyl group-containing polymerizable unsaturated monomers such as vinyl ether; Dialkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate; Glycidyl (meth) acrylate, (β-methyl) glycidyl (meth) acrylate, (meth) allyl glycidyl ether or polymerizable unsaturated carboxylic acids or mono-2- (meth) acryloyloxymonoethyl To various unsaturated carboxylic acids such as equimolar adducts of hydroxyl group-containing vinyl monomers such as phthalates and the above polycarboxylic acid anhydrides, "Epiclon 200", "Epiclon 400", "Epiclon 441", "Epiclon 850" or "Epi" Clone 1050 "(epoxy resin made by DIC Corporation) or" Epicoat 828 "," Epicoat 1001 "or" Epicoat 1004 "(epoxy resin by Japan Epoxy Resin Co., Ltd.)," Araldite 6071 " Or "Araldite6084" (epoxy resin manufactured by Chiba Co., Ltd. Switzerland), "Chison Knox 221" (epoxy compound manufactured by Chisso Co., Ltd.), or "Denacol EX-611" [Nagase Chemical Co., Ltd.] Shiki Kaisha epoxy compound Epoxy group-containing polymerizable unsaturated monomers such as epoxy group-containing polymerizable compounds obtained by addition reaction of various polyepoxy compounds having at least two epoxy groups in one molecule, such as equimolar ratios; and 2-hydroxyethyl (meth) acrylate- Isocyanate group containing (alpha), (beta)-ethylenically unsaturated monomers, such as a monomer which has isocyanate groups, such as hexamethylene diisocyanate diisocyanate and isocyanate ethyl (meth) acrylate, and a vinyl group; vinylethoxysilane, (alpha)-methacryloxypropyl Alkoxy silyl group containing polymerizability, such as trimethoxysilane, trimethyl siloxyethyl (meth) acrylate, and silicone type monomers, such as "KR-215, X-22-5002" (made by Shin-Etsu Chemical Co., Ltd.). Unsaturated monomers, and unsaturated mono- such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid or citraconic acid Or α, β-ethylenically unsaturated carboxylic acids such as dicarboxylic acids, monoesters of dicarboxylic acids and monohydric alcohols thereof, or 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) ) Acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3- Α, β- such as chloro-2-hydroxypropyl (meth) acrylate, di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl-monobutyl fumarate or polyethylene glycol mono (meth) acrylate Unsaturated carboxylic acid hydroalkyl esters, maleic acid, succinic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, benzenetricarboxylic acid, benzenetetracarboxylic acid, "hymic acid", tetrachlorophthalic acid or dodecenyl succinic acid, etc. Added with the polycarboxylic acid anhydride and the like carboxyl group-containing α, β- ethylenically unsaturated monomers, such as water.

Especially, use of C3 or less alkyl (meth) acrylates, such as methyl (meth) acrylate and ethyl (meth) acrylate, is preferable. Moreover, in order to change the surface characteristics of a pigment surface and to improve interaction with a pigment dispersant or a pigment dispersion resin, the polymerizable unsaturated monomer containing functional groups, such as at least 1 type of carboxy group, a sulfonic acid group, a phosphoric acid group, a hydroxyl group, a dimethylamino group, etc. It is preferable to copolymerize.

Moreover, in order not to elute the modified polyamine (B) and the polymer (P) from the pigment (A) at the time of use of a modified pigment (D), polymer (P) is still more preferable if it is bridge | crosslinked. As a polyfunctional polymerizable unsaturated monomer used as a crosslinking component, For example, divinylbenzene, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Polyethylene glycol di (meth) acrylate, 1,3-butanedioldi (meth) acrylate, 1,4-butanedioldi (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, neopentyl glycoldi Methacrylate, trimethylolpropane triethoxy tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerytate Lithol hexa (meth) acrylate, allyl methacrylate, etc. are mentioned.

In addition, other polymerizable unsaturated groups are used in a range in which a polymer containing a polymerizable unsaturated monomer (C) as an essential component, which is soluble in at least one of the above nonaqueous solvents and becomes insoluble or poorly soluble after polymerization, is not dissolved in the nonaqueous solvent system. You may use a monomer. As another polymerizable unsaturated monomer, the alkyl (meth) acrylate which has an alkyl group of 4 or more carbon atoms mentioned above, and the polymerizable unsaturated monomer which can be used other than the said alkyl (meth) acrylate are mentioned, for example.

The modified pigment (D) used in the present invention is at least one polymerizable unsaturated monomer (C) soluble in the nonaqueous solvent and insoluble or poorly soluble after polymerization in the presence of the pigment (A) and the modified polyamine (B). ) Is obtained by polymerizing.

It is preferable to mix a pigment (A) and a modified polyamine (B) before superposing | polymerizing.

By mixing, the surface of the pigment (A) is wetted with the modified polyamine (B), and the interface (formation of the pigment (A) with the modified polyamine (B)) formed by this is considered to be a field of polymerization, and the pigment ( After mixing A) and a modified polyamine (B), the said polymerizable unsaturated monomer (C) is further mixed and superposed | polymerized, and the modified pigment coated with the polymer (P) is obtained. Since this method does not make it necessary to form a finely and stably dispersed field of the pigment (A) as a dispersion stabilizer, surface treatment and the like of the pigment (A) for forming a finely dispersed state are not necessarily necessary. It is applicable to a kind of pigment.

As the mixing method, for example, a homogenizer, a disper, a bead mill, a paint shaker, a kneader, a roll mill, a ball mill, an attritor, a sand mill, or the like can be used. In the present invention, the form of the pigment to be used may be any type of slurry, wet cake, or powder. That is, in the manufacturing method of this invention, even the pigment containing water like a wet cake can be used.

After mixing the said pigment (A) and modified polyamine (B), a modified pigment (D) is obtained by further mixing and polymerizing a polymerizable unsaturated monomer (C) and the polymerization initiator mentioned later.

In that case, since the usage-amount of a modified polyamine (B) is optimized suitably according to the objective, there is no limitation in particular, Usually, 1-200 parts are used with respect to 100 parts of pigments (A), More preferably, it is 2-50 parts, More preferably Preferably it is 3-30 parts.

Moreover, since the usage-amount of the said polymerizable unsaturated monomer (C) is also optimized suitably according to the objective, there is no limitation in particular, Usually, 1-200 parts are used with respect to 100 parts of pigments (A), More preferably, 1-50 parts More preferably, it is 1-30 parts.

Finally, the amount of the modified polyamine (B) and the polymer (P) coated on the pigment is preferably 2 to 400 parts, more preferably 3 to 100 parts, further preferably 4 to 100 parts of the pigment (A). It is -60 parts. In that case, it is preferable to use at least 1 type of said polymerizable unsaturated monomer (C) in the ratio of 10-400 parts normally with respect to 100 parts of the said modified polyamine (B), Preferably it is 30-400 parts, Furthermore, Preferably it is 50-200 parts.

Although the method of superposing | polymerizing the said polymerizable unsaturated monomer (C) in presence of the said pigment (A), the said nonaqueous solvent, and a modified polyamine (B) may be performed by a well-known conventional polymerization method, it is normally present in the presence of a polymerization initiator. Under As such a polymerization initiator, azobisisobutyronitrile (AIBN), 2, 2- azobis (2-methylbutyronitrile), benzoyl peroxide, t-butylperbenzoate, t-butyl-2-ethylhexano Radical generation polymerization catalysts, such as an ate, t-butyl hydroperoxide, di-t-butyl peroxide, or cumene hydroperoxide, are used individually or in combination of 2 or more types.

Since a polymerization initiator may be hard to melt | dissolve in the said non-aqueous solvent system, the method of melt | dissolving in the said polymerizable unsaturated monomer (C) and adding to the mixed system of a pigment (A) and a modified polyamine (B) is preferable.

Moreover, although the said polymerizable unsaturated monomer (C) which melt | dissolved the said polymerizable unsaturated monomer (C) or a polymerization initiator can also be added by the dropping method in the state which reached | attained the polymerization temperature, it added in the state of normal temperature before temperature rising, and fully mixed The method of temperature rising and superposing | polymerizing afterwards is stable and preferable.

The polymerization temperature is usually in the range of 60 ° C to 130 ° C. In the case where the pigment (A) is an organic pigment, when the polymerization temperature is too high, morphological changes such as alteration and crystal growth of the pigment may be remarkable, and in that case, polymerization at 70 to 100 ° C is preferable.

After superposition | polymerization, the nonaqueous solvent etc. which were used for superposition | polymerization are removed by filtration, and it can obtain as a polymer coating pigment of powder by drying and pulverizing. A nutche, a filter press, etc. can be used for a filtration method. In addition, it can dry by well-known drying apparatuses, such as a box type drier, a vacuum drier, a band drier, and a spray drier. Moreover, well-known grinding | pulverization apparatuses, such as a mortar, a hand mill, a disk mill, a pin mill, and a jet mill, can be used for grinding | pulverization.

(Pigment Dispersion Composition for Color Filters)

The pigment dispersion composition for color filters of this invention is obtained by disperse | distributing a modified pigment (D) in the resin solution which mixed pigment dispersants, such as resin, and an organic solvent. In that case, a well-known conventional pigment dispersion method can be used and pigment dispersion can be performed using dispersers, such as a ball mill, a sand mill, a bead mill, a three roll mill, a paint conditioner, an attritor, a dispersion stirrer, and an ultrasonic wave. . As a specific dispersing apparatus, it is a super apex mill (made by Kotobuki Kien Kogyo Co., Ltd.), an ultra apex mill (made by Kotobuki Kien Kogyo Co., Ltd.), a dry steam PM-DCP stirring type bead mill apparatus (product made by Dreisukenke Co., Ltd.), a pico grain mill (Asada Teco ( Note) agent) etc. are mentioned.

As a grinding | polishing mediator used at the time of pigment dispersion, a grinding | polishing mediator made of a zirconia or a steel is mentioned, for example, Among these, the grinding media made from a zirconia excellent in abrasion resistance are especially preferable. Moreover, the range of 0.01-3.0 mm is preferable and, as for the diameter of a grinding medium, the range of 0.05-0.5 mm is especially preferable. If the diameter of the grinding media is larger than 3.0 mm, wet grinding is insufficient, which is not preferable.

As a pigment dispersant used at the time of pigment dispersion, the well-known pigment dispersant generally used for pigment dispersion can be used. For example, resin type dispersing agents, such as an intermediate or derivative of surfactant, a pigment, an intermediate or derivative of dye, or a polyamide resin, a polyurethane resin, polyester resin, and an acrylic resin, are mentioned. It is preferable to use polyester type and acrylic resin among the said various dispersing agents.

As a commercial item of a resin type dispersing agent, for example, "DISPERBYK-130", "DISPERBYK-161", "DISPERBYK-162", "DISPERBYK-163", "DISPERBYK-170", and "DISPERBYK-171" of BIC Chem. , "DISPERBYK-174", "DISPERBYK-180", "DISPERBYK-182", "DISPERBYK-183", "DISPERBYK-184", "DISPERBYK-185", "DISPERBYK-2000", "DISPERBYK-2001", " DISPERBYK-2020, DISPERBYK-2050, DISPERBYK-2070, DISPERBYK-2096, DISPERBYK-2150, Chiba Specialty Chemicals' EFKA1503, EFKA4010, EFKA4020, EFKA4300 , "EFKA4330", "EFKA4340", "EFKA4520", "EFKA4530", "EFKA5054", "EFKA7411", "EFKA7422", "EFKA7431", "EFKA7441", "EFKA7461", "EFKA7496", "EFKA7497" Solsol Spurs 3000, Solsol S9000 9000, Sol Spurs 13240, Sol Spurs 13650, Sol Spurs 13940, Sol Spurs 17000, Sol Spurs 18000 20000 '', `` Solfers 21000 '', `` Solfers 20000 '', `` Solfers 24000 '', `` Solfers 26000 '', `` Solfers 27000 '', `` Solfers 28000 '', `` Solfers 32000 '', `` Solfers 36000 '' Solsper 37000, Solsper 38000, Solsper 41000, Solsper 42000, Solsper 43000, Solsper 46000, Solsper 54000, Solsper 71000, Aji Spa PB-711, Aji Spa PB-821, Aji Spa PB-822, Aji Spa PB-814, and Aji Spa PB-824 from Ajinomoto Fine Techno Co., Ltd. It is possible to.

Moreover, a leveling agent, a coupling agent, cationic surfactant, etc. can also be used together. In this invention, these dispersing agents can also use 2 or more types together.

As an organic solvent used at the time of pigment dispersion, For example, aromatic solvents, such as toluene, xylene, and methoxybenzene, ethyl acetate, propyl acetate, butyl acetate, a propylene glycol monomethyl ether acetate, a propylene glycol monoethyl ether acetate, etc. Acetic acid ester solvents, propionate solvents such as ethoxyethyl propionate, alcohol solvents such as methanol and ethanol, butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl Ether solvents such as ether, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, aliphatic hydrocarbon solvents such as hexane, N, N-dimethylformamide, γ-butyrolactam, and N-methyl Nitrogen compound solvents, such as 2-pyrrolidone, aniline, and pyridine, lactone solvents, such as (gamma) -butyrolactone, methyl carbamate There may be mentioned carboxylic acid esters, water and the like, such as a 48:52 mixture of the carboxylic acid ethyl. Especially, water-soluble thing is preferable with polar solvents, such as a propionate, an alcohol type, an ether type, a ketone type, a nitrogen compound type, and a lactone type. When using a water-soluble organic solvent, water can also be used together. In this invention, these solvent can also use 2 or more types together.

Although there is no restriction | limiting in particular about each use ratio, Generally, 5-200 parts of pigment dispersants with respect to 100 parts of modified pigment (D), Preferably 10-100 pigment dispersants, More preferably, it is 10- Using the pigment dispersant of 60, the organic solvent is used so that the sum total of solid content of a modified pigment (D) and a pigment dispersant may be 10 to 25%, Preferably it is 10 to 20%.

(Color filter)

The pigment dispersion composition for color filters of this invention can be used for manufacture of the color filter which has each pixel part of red, green, blue, and a black matrix.

In manufacturing a color filter, all well-known manufacturing methods, such as the photolithographic method, the inkjet method, and the printing method, can be employ | adopted. Hereinafter, an example of the photolithography method will be described.

The photolithography method applies the photocurable composition which mixed the photocurable monomer, oligomer, photoinitiator, etc. suitably to the pigment dispersion composition for color filters of this invention to the surface of the side which provided the black matrix of the transparent substrate for color filters. After heat-drying (prebaking), pattern exposure is performed by irradiating ultraviolet-rays or visible light in the wavelength range of 200-500 nm through a photo mask, hardening the photocurable compound of the location corresponding to a pixel part, and then unexposed. A portion is developed with a developer to remove a non-pixel portion and to fix the pixel portion to a transparent substrate. By this method, the pixel part which consists of a cured coloring film of a photocurable composition is formed on a transparent substrate. A photocurable composition is produced for each of the black, red, green, and blue modified pigments (D), and the above operation is repeated to form a black matrix and to have red, green, and blue pixel parts at predetermined positions. Color filters can be produced.

In addition, yellow modified pigment (D) or purple modified pigment (D) can also be used together for formation of pixel parts, such as red, green, and blue. Moreover, you may heat-process (postbaking) the whole color filter after photocuring as needed.

As a method of apply | coating the said photocurable composition on transparent substrates, such as glass, a spin coating method, a roll coating method, the inkjet method, etc. are mentioned, for example. Moreover, although the heat-drying conditions of the photocurable composition after application | coating differ also with the kind, compounding ratio, etc. of each component, it is about 1 to 15 minutes at 50-150 degreeC normally.

Moreover, as a developing method after pattern exposure, the liquid method, the dipping method, the spray method, etc. are mentioned, for example. After exposure and image development of a photocurable composition, the transparent substrate in which the pixel part of the required color was formed was washed with water and dried.

The color filter obtained in this way is heat-processed (postbaking) at 100-280 degreeC for predetermined time with heating apparatuses, such as a hotplate and oven, and removes the volatile component in a coating film, and cured colored film of a photocurable composition. The unreacted photocurable compound remaining in the thermoset is thermoset to complete the color filter.

Although the manufacturing method of the color filter by the photolithographic method among the pigment dispersion methods was mentioned above, the color filter using the pigment dispersion composition for color filters of this invention is not limited to the said method, For example, electrodeposition method, transfer method, micelles You may manufacture by electrolysis, PVED (Photovoltaic Electrodeposition) method, etc.

[Example]

Hereinafter, an Example demonstrates this invention. Unless otherwise specified, "part" and "%" are mass references.

Synthesis Example 1 Synthesis of Vinyl Polymer (X1)

100 parts of xylene and 10 parts of thioglycolic acid are maintained at 80 ° C. in a nitrogen stream, while stirring 54 parts of methyl methacrylate, 36 parts of butyl acrylate, and a polymerization initiator (“Perbutyl (registered trademark) O” [active ingredient fur T-butyl oxy2-ethylhexanoate and Nippon Yushi Co., Ltd.] 2 parts were added dropwise over 4 hours. After completion of the dropwise addition, 0.5 part of "Perbutyl (trademark) O" was added every 4 hours, and it stirred at 80 degreeC for 12 hours. After completion of the reaction, xylene was added to adjust the nonvolatile content, thereby obtaining a xylene solution (X1) of a vinyl copolymer having a carboxyl group at one end having a nonvolatile content of 50%. The mass average molecular weight of this resin was 5000, and the acid value was 60.5 mgKOH / g.

Synthesis Example 2 Synthesis of Vinyl Polymer (X2)

100 parts of xylenes are maintained at 80 ° C. in a nitrogen stream, and 68 parts of ethyl methacrylate, 29 parts of 2-ethylhexyl methacrylate, 3 parts of thioglycolic acid, and a polymerization initiator (“Perbutyl (registered trademark) O [Active component peroxy 2-ethylhexanoate t-butyl, Nippon Yushi Co., Ltd.] 0.2 parts of a mixture was dripped over 4 hours. After completion of the dropwise addition, 0.5 part of "Perbutyl (trademark) O" was added every 4 hours, and it stirred at 80 degreeC for 12 hours. After completion of the reaction, xylene was added to adjust the nonvolatile content, thereby obtaining a xylene solution of a vinyl copolymer (X2) having a carboxyl group at one end having a nonvolatile content of 50%. The weight average molecular weight of this resin was 7000, the acid value was 18.0 mgKOH / g, and the glass transition temperature Tg was 38 degreeC.

Synthesis Example 3 Synthesis of Vinyl Polymer (X3)

100 parts of xylene are maintained at 80 ° C. in a nitrogen stream, and 66 parts of ethyl methacrylate, 28 parts of 2-ethylhexyl methacrylate, 6 parts of thioglycolic acid, and a polymerization initiator (“perbutyl (registered trademark) O [Active component peroxy 2-ethylhexanoate t-butyl, Nippon Yushi Co., Ltd.] 0.3 parts of a mixture was dripped over 4 hours. After completion of the dropwise addition, 0.5 part of "Perbutyl (trademark) O" was added every 4 hours, and it stirred at 80 degreeC for 12 hours. After completion of the reaction, an appropriate amount of xylene was added to adjust the nonvolatile content to obtain a xylene solution of a vinyl copolymer (X3) having a carboxyl group at one end of a nonvolatile content of 50%. The weight average molecular weight of this resin was 4000, the acid value was 36.0 mgKOH / g, and the glass transition temperature Tg was 38 degreeC.

Synthesis Example 4 Synthesis of Vinyl Polymer (X4)

100 parts of xylene are maintained at 80 ° C. in a nitrogen stream, and 66 parts of lauryl methacrylate, 28 parts of 2-ethylhexyl methacrylic acid, 6 parts of thioglycolic acid, and a polymerization initiator (“perbutyl (registered trademark)”) are stirred. O "[active component peroxy 2-ethylhexanoate t-butyl, Nippon Yushi Co., Ltd.] 0.15 parts of the mixture was dripped over 4 hours. After completion of the dropwise addition, 0.5 part of "Perbutyl (trademark) O" was added every 4 hours, and it stirred at 80 degreeC for 12 hours. After completion of the reaction, an appropriate amount of xylene was added to adjust the nonvolatile content to obtain a xylene solution of a vinyl copolymer (X4) having a carboxyl group at one end having a nonvolatile content of 50%. The weight average molecular weight of this resin was 4500, the acid value was 36.0 mgKOH / g, and the glass transition temperature Tg was -51 degreeC.

Synthesis Example 5 Synthesis of Vinyl Polymer (X5)

100 parts of xylenes are maintained at 80 ° C. in a nitrogen stream, and 94 parts of lauryl methacrylate, 6 parts of thioglycolic acid, and a polymerization initiator (“perbutyl (trademark) O” [active ingredient peroxy2-ethyl while stirring] A mixture consisting of 0.15 part of t-butyl hexanoate and Nippon Yushi Co., Ltd.) was added dropwise over 4 hours. After completion of the dropwise addition, 0.5 part of "Perbutyl (trademark) O" was added every 4 hours, and it stirred at 80 degreeC for 12 hours. After completion of the reaction, an appropriate amount of xylene was added to adjust the nonvolatile content to obtain a xylene solution of a vinyl copolymer (X5) having a carboxyl group at one end of a nonvolatile content of 50%. The weight average molecular weight of this resin was 5500, the acid value was 36.0 mgKOH / g and the glass transition temperature Tg was -65 degreeC.

Synthesis Example 6 Synthesis of Vinyl Polymer (X6)

100 parts of xylene are maintained at 80 ° C. in a nitrogen stream, and 94 parts of cetyl methacrylate, 6 parts of thioglycolic acid, and a polymerization initiator (“perbutyl (registered trademark) O” [active ingredient peroxy 2-ethylhexane while stirring) T-butyl acid, manufactured by Nippon Yushi Co., Ltd.]), was added dropwise over 4 hours. After completion of the dropwise addition, 0.5 part of "Perbutyl (trademark) O" was added every 4 hours, and it stirred at 80 degreeC for 12 hours. After completion of the reaction, an appropriate amount of xylene was added to adjust the nonvolatile content, thereby obtaining a xylene solution of a vinyl copolymer (X6) having a carboxyl group at one end having a nonvolatile content of 50%. The weight average molecular weight of this resin was 5000, and the acid value was 36.0 mgKOH /.

Synthesis Example 7 Synthesis of Vinyl Polymer (X7)

In a flask equipped with a stirrer, a reflux condenser, a nitrogen blowing tube, and a thermometer, 30 parts of ion-exchanged water and 30 parts of isopropyl alcohol were kept at 80 ° C. in a nitrogen stream, and 40 parts of N-vinylformamide and 2-mercaptoethanol were stirred. A mixture consisting of 8 parts and 0.8 part of a polymerization initiator ("perbutyl (trademark) O" [active component peroxy 2-ethylhexanoate t-butyl, Nippon Yushi Co., Ltd. product]) was dripped over 4 hours. After completion of the reaction, an appropriate amount of ion exchanged water was added to adjust the nonvolatile content, thereby obtaining a vinyl polymer (X7) having a nonvolatile content of 40%.

Synthesis Example 8 Synthesis of Polyvinylamine Copolymer (PA-1)

To a flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer, 125 parts of 40% non-volatile vinyl polymer (X7) obtained in Synthesis Example 7 and 141 parts of 20% sodium hydroxide solution were added, followed by stirring at 16 ° C. at 80 ° C. The reaction was time. After the reaction was completed, acetone was added to precipitate the resin powder, followed by separation and drying to obtain a solid content of the polyvinylamine copolymer (PA-1). The amine value of the polyvinylamine copolymer (PA-1) was 1174 mg KOH / g, and the hydrolysis rate of N-vinylformamide calculated from the amine number was 90%.

Synthesis Example 9 Synthesis of Polyvinylamine Copolymer (PA-2)

To a flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer, 125 parts of 40% non-volatile vinyl polymer (X7) obtained in Synthesis Example 7 and 42 parts of 20% sodium hydroxide solution were added thereto, followed by stirring at 80 ° C. The reaction was time. After completion of the reaction, acetone was added to precipitate the resin powder, followed by separation and drying to obtain a solid content of the polyvinylamine copolymer (PA-2). The amine value of the polyvinylamine copolymer (PA-2) was 305 mg KOH / g, and the hydrolysis rate of N-vinylformamide calculated from the amine number was 23%.

Synthesis Example 10 Synthesis of Modified Polyamine (BJ-1)

In a flask equipped with a stirrer, a reflux condenser, a nitrogen intake tube, and a thermometer, a mixture consisting of 100 parts of xylene and a 20% aqueous solution of polyallylamine ("PAA-05" manufactured by Nitto Boseiki Co., Ltd., number average molecular weight approximately 5,000) 37.5 parts Was charged and stirred at 140 ° C while stirring under a nitrogen stream, the water was distilled off using a separation device, and the xylene was returned to the reaction solution to obtain this in Synthesis Example 1 The thing which heated up 168.8 parts of vinyl copolymers (X1) (used as a vinyl copolymer (B-1) in this application) to 140 degreeC was added, and reaction was performed at 140 degreeC for 8 hours. After completion of the reaction, an appropriate amount of xylene was added to adjust the nonvolatile content, thereby obtaining a modified polyamine (BJ-1) having a nonvolatile content of 40%. The mass average molecular weight of this resin was 7,500, and the amine value was 32.5 mg KOH / g.

Synthesis Example 11 Synthesis of Modified Polyamine (BJ-2)

19.0 parts of vinyl copolymer (X2) (used as vinyl copolymer (B-1) in the present application) obtained in 54.5 parts of xylene and Synthesis Example 2 in a flask equipped with a stirrer, a reflux condenser, a nitrogen blowing tube, and a thermometer; 38.0 parts of vinyl copolymer (X3) obtained by the synthesis example 3 (used as a vinyl copolymer (B-2-1) in this application), and 20% of polyallylamine aqueous solution (made by Nitto Bosei Co., Ltd. "PAA- 05 ", number average molecular weight about 5,000) Charge the mixture which consists of 7.5 parts, and it stirred at 140 degreeC, stirring under nitrogen stream, and distilled water using a separator, and while returning xylene to a reaction solution for 8 hours 140 The reaction was carried out at 占 폚.

After completion of the reaction, an appropriate amount of xylene was added to adjust the nonvolatile content to obtain a modified polyamine (BJ-2) having a nonvolatile content of 40%. The weight average molecular weight of this resin was 10,000, and the amine number was 22.0 mg KOH / g.

Synthesis Example 12 Synthesis of Modified Polyamine (BJ-3)

10.5 parts of polyallylamine 20% aqueous solution "PAA-03" and polyethyleneglycol polypropylene glycol monomethacrylate ("Blemmer" made by Nichiyu Co., Ltd.) to a flask equipped with a stirrer, a reflux condenser, a nitrogen blowing tube, and a thermometer. 70PEP-350B ", average ethylene glycol chain number 5, average propylene glycol chain number 2) (used as (meth) acrylate (B-3) in this application) 1.5 parts are charged, and it stirred at 50 degreeC, stirring under nitrogen stream. It was made to react for 3 hours. Subsequently, 35.2 parts of xylene and 52.8 parts of vinyl copolymer (X3) obtained in Synthesis Example 3 (used as the vinyl copolymer (B-1) in the present application) were charged, stirred at 140 ° C while stirring under a nitrogen stream, and a separation device. The reaction was carried out at 140 ° C. for 8 hours while the water was distilled off and the xylene was returned to the reaction solution. After completion of the reaction, an appropriate amount of xylene was added to adjust the nonvolatile content to obtain a modified polyamine (BJ-3) having a nonvolatile content of 40%. The weight average molecular weight of this resin was 8,000, and the amine number was 31.0 mg KOH / g.

Synthesis Example 13 Synthesis of Modified Polyamine (BJ-4)

To a flask equipped with a stirrer, a reflux condenser, a nitrogen blowing tube, and a thermometer, 100 parts of a modified polyamine (BJ-3) having a nonvolatile content of 40% obtained in Synthesis Example 12 and 1.6 parts of glycidyl methacrylate were added thereto, and the mixture was heated at 80 ° C. The reaction was time. After completion of the reaction, an appropriate amount of xylene was added to adjust the nonvolatile content to obtain a modified polyamine (BJ-4) having a nonvolatile content of 40%.

Synthesis Example 14 Synthesis of Modified Polyamine (BJ-5)

To a flask equipped with a stirrer, a reflux condenser, a nitrogen intake tube, and a thermometer, 11 parts of xylene and 7.5 parts of polyethyleneimine (epomine SP-006, manufactured by Nihon Shokubai Chemical Co., Ltd., average molecular weight of about 600) were added to the flask with nitrogen. While stirring, the mixture was stirred at 140 ° C, water was distilled off using a separation device, and xylene was returned to the reaction solution, while the vinyl copolymer (X1) obtained in Synthesis Example 1 was added thereto (the vinyl copolymer in the present application). It used as (B-1)) What heated up 168.8 parts to 140 degreeC, and reacted at 140 degreeC for 8 hours. After completion of the reaction, an appropriate amount of xylene was added to adjust the nonvolatile content to obtain a modified polyamine (BJ-5) having a nonvolatile content of 40%.

Synthesis Example 15 Synthesis of Modified Polyamine (BJ-6)

11 parts of xylenes and 7.5 parts of polyvinylamine copolymers (PA-1) obtained in Synthesis Example 8 were added to a flask equipped with a stirrer, a reflux condenser, a nitrogen blowing tube, and a thermometer, stirred at 140 ° C. while stirring under a nitrogen stream, and separated. 152 parts of vinyl copolymer (X1) (used as a vinyl copolymer (B-1) in this application) obtained by the synthesis example 1 while water was distilled using an apparatus and refluxing xylene in the reaction solution What heated up to 140 degreeC was added, and reaction was performed at 140 degreeC for 8 hours. After completion of the reaction, an appropriate amount of xylene was added to the water in the reaction solution for nonvolatile content adjustment to obtain a modified polyamine (BJ-6) having a nonvolatile content of 40%.

Synthesis Example 16 Synthesis of Modified Polyamine (BJ-7)

11 parts of xylenes and 7.5 parts of polyvinylamine copolymers (PA-2) obtained in Synthesis Example 9 were added to a flask equipped with a stirrer, a reflux condenser, a nitrogen blowing tube, and a thermometer, stirred at 140 ° C. while stirring under a nitrogen stream, and separated. 42.2 parts of vinyl copolymer (X1) (used as a vinyl copolymer (B-1) in this application) obtained in the synthesis example 1 was carried out, while water was distilled using an apparatus and xylene was returned to the reaction solution. What heated up to 140 degreeC was added, and reaction was performed at 140 degreeC for 8 hours. After completion of the reaction, an appropriate amount of xylene was added to the water in the reaction solution for nonvolatile content adjustment to obtain a modified polyamine (BJ-7) having a nonvolatile content of 40%.

Synthesis Example 17 Synthesis of Modified Polyamine (BJ-8)

In a flask equipped with a stirrer, a reflux condenser, a nitrogen intake tube, and a thermometer, a mixture consisting of 100 parts of xylene and a 20% aqueous solution of polyallylamine ("PAA-05" manufactured by Nitto Boseiki Co., Ltd., number average molecular weight approximately 5,000) 37.5 parts 172.5 parts of the vinyl copolymer (X4) obtained in Synthesis Example 4 was charged while stirring at 140 ° C while stirring under a nitrogen stream, distilling water using a separator, and returning xylene to the reaction solution. What heated up to 140 degreeC (used as a vinyl copolymer (B-1) in this application) was added, and reaction was performed at 140 degreeC for 8 hours. After completion of the reaction, an appropriate amount of xylene was added to adjust the nonvolatile content to obtain a modified polyamine (BJ-8) having a nonvolatile content of 40%. The mass average molecular weight of this resin was 6,200, and the amine value was 46.0 mg KOH / g.

Synthesis Example 18 Synthesis of Modified Polyamine (BJ-9)

A mixture comprising 100 parts of xylene and 20% aqueous solution of polyallylamine ("PAA-05" manufactured by Nitto Boseki Co., Ltd., number average molecular weight about 5,000) in a flask equipped with a stirrer, a reflux condenser, a nitrogen intake tube, and a thermometer. 75 parts of the vinyl copolymer (X2) obtained in Synthesis Example 2 while charging the product, stirring at 140 ° C while stirring under a nitrogen stream, distilling water using a separator, and returning xylene to the reaction solution. (Used as a vinyl copolymer (B-1) in this application) and 99.4 parts of vinyl copolymers (X5) obtained by the synthesis example 5 were heated up to 140 degreeC, and reaction was performed at 140 degreeC for 8 hours. After completion of the reaction, an appropriate amount of xylene was added to adjust the nonvolatile content to obtain a modified polyamine (BJ-9) having a nonvolatile content of 40%. The mass average molecular weight of this resin was 7,000, and the amine value was 35.7 mg KOH / g.

Synthesis Example 19 Synthesis of Modified Polyamine (BJ-10)

A mixture comprising 100 parts of xylene and 20% aqueous solution of polyallylamine ("PAA-05" manufactured by Nitto Boseki Co., Ltd., number average molecular weight about 5,000) in a flask equipped with a stirrer, a reflux condenser, a nitrogen intake tube, and a thermometer. 174.4 parts of the vinyl copolymer (X6) obtained in Synthesis Example 6 was charged while stirring at 140 ° C while stirring under a nitrogen stream, distilling water using a separator, and returning xylene to the reaction solution. What heated up to 140 degreeC (used as a vinyl copolymer (B-1) in this application) was added, and reaction was performed at 140 degreeC for 8 hours. After completion of the reaction, an appropriate amount of xylene was added to adjust the nonvolatile content to obtain a modified polyamine (BJ-10) having a nonvolatile content of 40%. The mass average molecular weight of this resin was 8,000, and the amine value was 31.7 mg KOH / g.

Comparative Synthesis Example 1 Synthesis of Polymer (BH-1)

In a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen gas introduction tube, 800 parts of heptane and 170 parts of butyl acetate were charged, the temperature was raised to 90 ° C, and at the point where the temperature reached the same temperature, 950 of 2ethylhexyl acrylate. In addition, a mixture consisting of 50 parts of dimethylaminoethyl methacrylate and 7 parts of 2,2'-azobis (2-methylbutyronitrile) was added dropwise over 5 hours, and maintained at the same temperature for 10 hours even after the completion of dropping. By continuing to react. Thereafter, a solution obtained by dissolving 0.2 parts of t-butyl pyrocatechol in 15 parts of butyl acetate was added, and after adding 15 parts of glycidyl methacrylate and 30 parts of dimethylaminoethanol, the temperature was raised to 80 ° C. By reacting at temperature for 10 hours, the solution of the polymer (BH-1) containing the polymerizable unsaturated group soluble in a nonaqueous solvent was obtained.

Modification Example 1 Synthesis of Modified Pigment (1)

C.I. 200 parts of the wet cake (50% of pigment content) of Pigment Green 58, 10 parts of the modified polyamine (BJ-1) obtained in Synthesis Example 10 as a solid content, 400 parts of 1.25 mm zirconia beads, 200 parts of heptanes The mixture was put in a bottle and mixed for 90 minutes with a paint shaker (Toyo Seiki Co., Ltd.). After dilution with 100 parts of heptane, zirconia beads were removed to prepare a pigment mixture.

400 parts of the obtained pigment mixture was charged into a separable flask equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen gas introduction tube, and then 2 parts of t-butylacrylamide sulfonic acid dissolved in 20 parts of ion-exchanged water was added thereto. What melt | dissolved 2 parts of 2,2'- azobis (2-methylbutyronitrile) was added to the polymerizable monomer composition of 3 parts of methyl methacrylate and 5 parts of ethylene glycol dimethacrylate. After stirring continued at room temperature for 30 minutes, it heated up at 80 degreeC and continued reaction at the same temperature for 15 hours. After temperature reduction, the polymer treatment pigment and the polymerization solvent were separated by filtration. After drying the obtained polymer pigment at 100 degreeC with a hot air dryer for 5 hours, the modified pigment (1) was obtained by grind | pulverizing with a grinder.

Synthesis of Modified Examples 2 to 21 Modified Pigments (2) to (21)

The pigment mixture liquid was created like Example 1 except having changed the pigment (A) and modified polyamine (BJ-1) to be used into the pigment of Tables 1-5, and modified polyamine (B).

Modified pigments (2) to (21) in the same manner as in Example 1 except that the polymerizable monomer (C) was changed to the polymerizable monomer (C) shown in Tables 1 to 5 using 400 parts of the obtained pigment mixed liquid. Got.

TABLE 1

(C.I. Pigment Green 58): C.I. Pigment Green 58 wet cake (for 50% pigment)

(C.I. Pigment Red 254): C.I. Pigment Red 254 Powder

(C.I. Pigment Blue 15: 6): C.I. Pigment Blue 15: 6 Powder

(C.I. Pigment yellow 150): C.I. Pigment Yellow 150 Powder

TABLE 2

(C.I. Pigment Green 58): C.I. Pigment Green 58 wet cake (for 50% pigment)

[Table 3]

(C.I. Pigment Green 58): C.I. Pigment Green 58 wet cake (for 50% pigment)

[Table 4]

(C.I. Pigment Green 58): C.I. Pigment Green 58 wet cake (for 50% pigment)

TABLE 5

PG58: C.I. Pigment Green 58 wet cake (for 50% pigment)

Comparative Example 1

C.I. 192 parts of the wet cake (52% pigment) of Pigment Green 58, 5 parts of the polymer (BH-1) obtained in Comparative Synthesis Example 1 as solids, 400 parts of 1.25 mm zirconia beads, 200 parts of heptanes It put in the bottle, and mixed for 90 minutes with the paint shaker (Toyo Seiki Co., Ltd.). After dilution with 100 parts of heptane, zirconia beads were removed. 400 parts of the obtained pigment mixture was charged into a separable flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen gas introduction tube, and then, while stirring, 2 parts of t-butylacrylamide sulfonic acid dissolved in 20 parts of ion-exchanged water was added thereto. What melt | dissolved 2 parts of 2,2'- azobis (2-methylbutyronitrile) was added to the polymerizable monomer composition of 5 parts of ethylene glycol dimethacrylate and 3 parts of butyl methacrylates. After stirring continued at room temperature for 30 minutes, it heated up at 80 degreeC and continued reaction at the same temperature for 15 hours. After temperature reduction, the polymer treatment pigment and the polymerization solvent were separated by filtration. After the obtained polymer pigment was dried at 100 degreeC for 5 hours by the hot air dryer, the comparative modified pigment (1) was obtained by grind | pulverizing with a grinder.

Example 1 Preparation of Pigment Dispersion Liquid 1 and Color Filter

A solution in which 5 parts of the modified pigment (1) obtained in Modification Example 1 and 1.5 parts of Azispa PB-821 (a pigment dispersant manufactured by Ajinomoto Fine Techno Co., Ltd.) were dissolved in 26.8 parts of propylene glycol monomethyl ether acetate (hereinafter PGMAc), 65 parts of 0.5 mm zirconia beads were put into a polyethylene photosphere bottle and dispersed for 2 hours with a paint shaker (Toyo Seiki Co., Ltd.), then zirconia beads were removed to obtain a pigment dispersion (1). 75.00 parts of pigment dispersion liquid and 5.50 parts of polyester acrylate resin (made by Aronix M7100, manufactured by Toagosei Chemical Co., Ltd.) 1.00 parts of benzophenone (KAYACURE BP-100, manufactured by Nippon Kayaku Co., Ltd.) and 13.5 parts of Yukaester EFP were stirred with a dispersion stirrer, filtered through a filter having a pore size of 1.0 μm, thereby obtaining a pigment dispersion resist (color resist). . The pigment dispersion resist was applied to a 1 mm thick glass using a spectrophotometer MCPD-3000 manufactured by Otsuka Denshi Co., Ltd. to calculate the chromaticity coordinate y value at the C2 light source side color, and applied using a spin coater so that y = 0.48. After preliminary drying for 5 minutes at 60 ℃ to form a coating film. Subsequently, after exposing the pattern by an ultraviolet-ray through a photo mask, the unexposed part was wash | cleaned in 0.5% of sodium carbonate aqueous solution, it wash | cleaned further with pure water, and then the obtained coating film was heated at 230 degreeC for 15 minutes, and hardened a coating film. It was made into the color filter. Thus, the viscosity of the pigment dispersion liquid 1 obtained, the brightness | luminance, and contrast of a color filter pixel part were evaluated by the following method, and it was shown in Table 6.

(Viscosity)

Viscosity was measured using the Brookfield company "Digital Viscometer DV-II Pro." Generally, the lower the viscosity of the dispersion is preferable.

(Luminance)

The luminance (Y value) measured the Y value in CIE colorimeter chromaticity by the C2 light source side color using the Otsuka Denshi Co., Ltd. spectrophotometer MCPD-3000. In this case, the higher the luminance (Y value), the higher the visual brightness.

(Contrast)

The said color filter pixel part was provided between two polarizing plates, the light source was provided on one side, and the CCD camera was installed on the opposite side, and the brightness was measured. It calculated from the ratio of the luminance (transmitted light intensity) between when the polarization axes became parallel and when they became perpendicular.

<Example 2, 3, 7-21>

Pigment dispersion | distribution, coating, and evaluation were performed by the method similar to Example 1 except having changed the modified pigment 1 as Table 6 and Table 7.

Example 4 Preparation of Pigment Dispersion 4 and Color Filter

5 parts of the modified pigment (4) obtained in the modified example 4 and 1.5 parts of Azispa PB-821 (a pigment dispersant manufactured by Ajinomoto Fine Techno Co., Ltd.) were dissolved in 26.8 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAc), 65 parts of 0.5 mm zirconia beads were put into a polyethylene photosphere bottle and dispersed for 2 hours with a paint shaker (Toyo Seiki Co., Ltd.), then zirconia beads were removed to obtain a pigment dispersion (4). 75.00 parts of pigment dispersion liquid and 5.50 parts of polyester acrylate resin (made by Aronix M7100, manufactured by Toagosei Chemical Co., Ltd.) 1.00 parts of benzophenone (KAYACURE BP-100, manufactured by Nippon Kayaku Co., Ltd.) and 13.5 parts of Yukaester EFP were stirred with a dispersion stirrer, filtered through a filter having a pore size of 1.0 μm, thereby obtaining a pigment dispersion resist (color resist). . The pigment dispersion resist was applied to a 1 mm thick glass using a spectrophotometer MCPD-3000 manufactured by Otsuka Denshi Co., Ltd. to calculate the chromaticity coordinate y value from the C2 light source side color, and applied using a spin coater so that y = 0.107. After preliminary drying for 5 minutes at 60 ℃ to form a coating film. Subsequently, after exposing the pattern by an ultraviolet-ray through a photo mask, the unexposed part was wash | cleaned in 0.5% of sodium carbonate aqueous solution, it wash | cleaned further with pure water, and then the obtained coating film was heated at 230 degreeC for 15 minutes, and hardened a coating film. It was made into the color filter. Thus, the viscosity of the pigment dispersion liquid 5 obtained, the brightness | luminance, and contrast of a color filter pixel part were evaluated by the following method, and it was shown in Table 6.

Example 5 Preparation of Pigment Dispersion 5 and Color Filter

5 parts of the modified pigment (5) obtained in the modified example 5 and 1.5 parts of Azispa PB-821 (a pigment dispersant manufactured by Ajinomoto Fine Techno Co., Ltd.) were dissolved in 26.8 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAc), 65 parts of 0.5 mm zirconia beads were put into a polyethylene photosphere bottle and dispersed for 2 hours with a paint shaker (Toyo Seiki Co., Ltd.), then zirconia beads were removed to obtain a pigment dispersion (5). 75.00 parts of pigment dispersion liquid and 5.50 parts of polyester acrylate resin (made by Aronix M7100, manufactured by Toagosei Chemical Co., Ltd.) 1.00 parts of benzophenone (KAYACURE BP-100, manufactured by Nippon Kayaku Co., Ltd.) and 13.5 parts of Yukaester EFP were stirred with a dispersion stirrer, filtered through a filter having a pore size of 1.0 μm, thereby obtaining a pigment dispersion resist (color resist). . The pigment dispersion resist was coated on a 1 mm thick glass using a spectrophotometer MCPD-3000 manufactured by Otsuka Denshi Co., Ltd., using a spin coater to calculate the chromaticity coordinate x value at the C2 light source side color such that x = 0.64. After preliminary drying for 5 minutes at 60 ℃ to form a coating film. Subsequently, after exposing the pattern by an ultraviolet-ray through a photo mask, the unexposed part was wash | cleaned in 0.5% of sodium carbonate aqueous solution, it wash | cleaned further with pure water, and then the obtained coating film was heated at 230 degreeC for 15 minutes, and hardened a coating film. It was made into the color filter. Thus, the viscosity of the pigment dispersion liquid 5 obtained, the brightness | luminance, and contrast of a color filter pixel part were evaluated by the following method, and it was shown in Table 6.

Example 6 Preparation of Pigment Dispersion 6 and Color Filter

5 parts of the modified pigment (6) obtained in the modified example 6 and 1.5 parts of azispa PB-821 (pigment dispersant manufactured by Ajinomoto Fine Techno Co., Ltd.) were dissolved in 26.8 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAc), 65 parts of 0.5 mm zirconia beads were put into a polyethylene photosphere bottle and dispersed for 2 hours with a paint shaker (Toyo Seiki Co., Ltd.), then zirconia beads were removed to obtain a pigment dispersion (6). 75.00 parts of pigment dispersion liquid and 5.50 parts of polyester acrylate resin (made by Aronix M7100, manufactured by Toagosei Chemical Co., Ltd.) 1.00 parts of benzophenone (KAYACURE BP-100, manufactured by Nippon Kayaku Co., Ltd.) and 13.5 parts of Yukaester EFP were stirred with a dispersion stirrer, filtered through a filter having a pore size of 1.0 μm, thereby obtaining a pigment dispersion resist (color resist). . The pigment dispersion resist was coated on a 1 mm thick glass using a spectrophotometer MCPD-3000 manufactured by Otsuka Denshi Co., Ltd., using a spin coater to calculate the chromaticity coordinate x value at the C2 light source side color such that x = 0.45. After preliminary drying for 5 minutes at 60 ℃ to form a coating film. Subsequently, after exposing the pattern by an ultraviolet-ray through a photo mask, the unexposed part was wash | cleaned in 0.5% of sodium carbonate aqueous solution, it wash | cleaned further with pure water, and then the obtained coating film was heated at 230 degreeC for 15 minutes, and hardened a coating film. It was made into the color filter. Thus, the viscosity of the pigment dispersion liquid 6 obtained, the brightness | luminance, and contrast of a color filter pixel part were evaluated by the following method, and it was shown in Table 6.

<Comparative Examples 1, 5>

Pigment dispersion | distribution, coating, and evaluation were performed by the method similar to Example 1 except having changed the modified pigment 1 as shown in Table 7.

Comparative Example 2

Pigment dispersion | distribution, coating, and evaluation were performed by the method similar to Example 4 except having changed the modified pigment 4 as shown in Table 7.

Comparative Example 3

Pigment dispersion | distribution, coating, and evaluation were performed by the method similar to Example 5 except having changed the modified pigment 5 as shown in Table 7.

Comparative Example 4

Pigment dispersion | distribution, coating, and evaluation were performed by the method similar to Example 6 except having changed the modified pigment 6 as shown in Table 7.

TABLE 6

TABLE 7

(Measurement of Retardation Value)

The retardation value of the color filter obtained in Examples 19-21 was measured. The retardation value uses the spectroscopic ellipsometer "M-2000X" made by JA Woollam Co., Ltd., and measures the amplitude Ψ and phase difference Δ between wavelengths 245 to 1000 nm at the incident angle of 0 degrees and 45 degrees of the color filter pixel portion. Measured. Based on this, the retardation value Rth in 550 nm was computed, and the value converted into the film thickness of 2 micrometers was described.

[Table 8]

As a result, the brightness | luminance and contrast of the color filter pixel part using modified pigments (1)-(21) became high compared with the comparative examples 1-4 using the pigment which is not modified | denatured. In addition, Comparative Example 5 is C.I. Although Pigment Green 58 is an example using a polymer containing a polymerizable unsaturated group soluble in a non-aqueous solvent as a modified pigment, the color filter of Example 1 gives higher contrast.

In addition, the color filters using the modified pigments 19 to 21 were able to greatly reduce the retardation value in comparison with Comparative Example 1 using the pigment that is not modified.

Claims (4)

As a pigment dispersion composition for color filters containing a colorant, resin, and the organic solvent which can melt | dissolve the said resin, As said colorant,
On the pigment (A) surface,
Modified polyamine (B) which reacted the vinyl copolymer (B-1) which has the functional group which reacts with an amino group to form an amide bond at one end, and was made to react with the amino group of a polyamine,
Polymer (P) obtained by polymerizing at least one polymerizable unsaturated monomer (C) that is soluble in a nonaqueous solvent and insoluble or poorly soluble after polymerization.
Pigment dispersion composition for color filters, characterized by using a modified pigment (D) having a. The method of claim 1,
The pigment dispersion composition for color filters whose said polyamine is at least 1 sort (s) chosen from the group which consists of polyallylamine, polyvinylamine, and polyethyleneimine. The method according to claim 1 or 2,
The pigment dispersion composition for color filters whose said pigment (A) is CI pigment green 58. The color filter pigment dispersion composition as described in any one of Claims 1-3 is used.